TW201840699A - Resin film for electronic devices, and electronic device - Google Patents

Abstract

Provided is a resin film for electronic devices, which contains a resin containing a polymer, moisture-absorbing particles that are dispersed in the resin and have primary particle diameters of 200 nm or less, and a dispersant, and wherein the absolute value of the difference between the refractive index of the resin and the refractive index of the particles is 0.05 or less. The resin is preferably a thermoplastic resin, and is more preferably a thermoplastic elastomer. The polymer is preferably one or more copolymers selected from among aromatic vinyl compound-conjugated diene copolymers and hydrogenated aromatic vinyl compound-conjugated diene copolymers. Also provided is an electronic device which is provided with this resin film for electronic devices.

Description

Resin film for electronic device and electronic device

The present invention relates to a resin film for an electronic device and an electronic device.

In electronic devices such as organic electroluminescence devices (hereinafter sometimes referred to as “organic EL light-emitting devices” as appropriate), resin films are used for purposes such as sealing. As an example of such a resin film for an electronic device, a film having high adhesion to a substrate interface to prevent moisture from entering the light-emitting layer of the organic EL light-emitting device has been examined.

As such a film, a bonding film having a bonding agent layer containing a hygroscopic filler as part of the bonding agent layer has been proposed to further improve the effect of preventing moisture from entering the light-emitting layer and the like (see Patent Document 1: Japan). Patent Publication No. 2015-504457 (corresponding publication: US Patent Application Publication No. 2014/091296).

In many cases, a film including a layer containing hygroscopic particles includes a hygroscopic agent and an additive for dispersing the hygroscopic agent. Therefore, the adhesion to the device may be hindered. In addition, depending on the hygroscopic agent used, the haze may increase and the transparency required in the device may not be achieved.

Therefore, an object of the present invention is to provide a resin film for an electronic device having high transparency and high adhesion to the device, and an electronic device including the resin film.

The present inventors have conducted studies in order to solve the aforementioned problems. As a result, the present inventors have found that by including a polymer-containing resin with particles and dispersants "that are hygroscopic particles of a specific particle size and the difference in refractive index from the resin is within a specific range," both transparency can be obtained. A resin film for electronic devices with good adhesion and adhesion, and the present invention has been completed.

That is, the present invention is as follows.

[1] A resin film for an electronic device, comprising: a polymer-containing resin, hygroscopic particles dispersed in the resin and having a primary particle diameter of 200 nm or less, and a dispersant, wherein the refractive index of the resin is the same as that of the resin The absolute value of the difference between the particles is 0.05 or less.

[2] The resin film for an electronic device according to [1], wherein the resin is a thermoplastic resin.

[3] The resin film for an electronic device according to [2], wherein the thermoplastic resin is a thermoplastic elastomer.

[4] The resin film for an electronic device according to any one of [1] to [3], wherein the polymer is selected from an aromatic vinyl compound-conjugated diene copolymer and a hydrogenated aromatic vinyl compound -One or more conjugated diene copolymers.

[5] The resin film for an electronic device according to [4], wherein the aromatic vinyl compound-conjugated diene copolymer is an aromatic vinyl compound-conjugated diene block copolymer.

[6] The resin film for electronic devices according to [5], wherein the aromatic vinyl compound-conjugated diene block copolymer is selected from the group consisting of styrene-butadiene block copolymer and styrene-butadiene One or more of an olefin-styrene block copolymer, a styrene-isoprene block copolymer, and a styrene-isoprene-styrene block copolymer.

[7] The resin film for an electronic device according to [4], wherein the hydrogenated aromatic vinyl compound-conjugated diene copolymer is a hydrogenated aromatic vinyl compound-conjugated diene block copolymer.

[8] The resin film for electronic devices according to [7], wherein the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is selected from hydrogenated styrene-butadiene block copolymer, hydrogenated One or more of a styrene-butadiene-styrene block copolymer, a hydrogenated styrene-isoprene block copolymer, and a hydrogenated styrene-isoprene-styrene block copolymer.

[9] The resin film for an electronic device according to [7] or [8], wherein the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is an unsaturated bond of a conjugated diene and an aromatic ring. A hydrogenated aromatic vinyl compound-conjugated diene block copolymer.

[10] The resin film for an electronic device according to any one of [1] to [8], wherein the resin includes a polymer having a polar group as the polymer.

[11] The resin film for an electronic device according to [10], wherein the polymer having a polar group is a graft polymer containing a unit containing a polar group.

[12] The resin film for electronic devices according to any one of [1] to [11], having a storage elastic modulus at 25 ° C of 10 ⁷ Pa or more and 10 ⁹ Pa or less.

[13] The resin film for an electronic device according to any one of [1] to [12], which has a thickness of 0.1 μm or more and 1000 μm or less.

[14] The resin film for electronic devices according to any one of [1] to [13], wherein the internal haze is 6.0% or less.

[15] An electronic device including the resin film for an electronic device according to any one of [1] to [14].

The resin film for an electronic device of the present invention can be used as a resin film for an electronic device. By using such a resin film, it is possible to have both high transparency and high adhesion to the device.

In addition, the electronic device of the present invention can be made into a device that has the transparency required when it is used as a display and prevents the intrusion of moisture by using a resin film having both high transparency and high adhesion.

The embodiments and examples are disclosed below to explain the present invention in detail. However, the present invention is not limited to the implementation modes and examples disclosed below, and can be implemented with arbitrary changes without departing from the scope of the patent application of the present invention and its equivalent scope.

[1. Overview of resin film for electronic devices]

The resin film (hereinafter also referred to as a "resin film") for an electronic device of the present invention includes a polymer-containing resin, hygroscopic particles dispersed in the resin, and having a primary particle diameter of 200 nm or less (hereinafter sometimes referred to as "resin film"). Particles are simply referred to as "hygroscopic particles") and dispersants. The absolute value of the difference between the refractive index of the resin contained in the resin film of the present invention and the hygroscopic particles is 0.05 or less.

[2. Resin]

In the present invention, as the polymer-containing resin, a thermoplastic resin is preferred in terms of ease of molding. As such a thermoplastic resin, a thermoplastic elastomer is preferable from the viewpoint that it is easy to be formed and is unlikely to break.

The term "thermoplastic elastomer" refers to a material that exhibits the characteristics of rubber at room temperature and is plasticized at high temperature to be capable of being molded. This kind of thermoplastic elastomer has the characteristics that it is difficult to produce elongation and fracture under the load of a small force. Specifically, the thermoplastic elastomer exhibits values of Young's modulus of 0.001 to 1 GPa and a tensile elongation (elongation at break) of 100 to 1000% at 23 ° C. In addition, in the high temperature range of 40 ° C to 200 ° C, the thermoplastic elastomer softens, the storage elastic modulus decreases rapidly, and the tangent tan δ (loss elastic modulus / storage elastic modulus) is lost, or has a peak value, or appears to exceed 1. value. The Young's modulus and tensile elongation can be measured in accordance with JIS K7113. In addition, the loss tangent tanδ can be measured by a commercially available dynamic viscoelasticity measuring device.

The thermoplastic elastomer generally does not contain a residual solvent, and even if it contains a residual solvent, its amount is small, and therefore there is little outgassing. Therefore, it is difficult to generate a gas in a low-pressure environment, so that the resin film itself can be prevented from being a source of gas generation. In addition, unlike thermosetting resins or photocurable resins, since a treatment for crosslinking is not required in the manufacturing process, steps can be simplified.

[2.1. Polymer]

The resin contains a polymer as a main component.

Examples of polymers include ethylene-α-olefin copolymers such as ethylene-propylene copolymers; ethylene-α-olefin-polyene copolymers; ethylene and ethylene such as methyl methacrylate and ethylene-butyl acrylate; Copolymers of unsaturated carboxylic acid esters; copolymers of ethylene and fatty acid vinyl esters such as ethylene-vinyl acetate; acrylic acid such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate Alkyl ester polymer; polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylate copolymer Diene copolymers such as butadiene-alkyl (meth) acrylate-acrylonitrile copolymer, butadiene-alkyl (meth) acrylate-acrylonitrile-styrene copolymer; butene-isoprene Styrene copolymer; styrene-butadiene random copolymer, styrene-isoprene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, Styrene-isoprene block copolymer, styrene -Isoprene-styrene block copolymers and other aromatic vinyl compounds-conjugated diene copolymers; hydrogenated styrene-butadiene random copolymers, hydrogenated styrene-isoprene random copolymers, hydrogenated benzene Ethylene-butadiene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-isoprene-styrene block copolymer Segmented copolymers such as hydrogenated aromatic ethylene compounds-conjugated diene copolymers; and low-crystalline polybutadiene, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, and ethylene-based ionic polymers. The polymer may be used singly or in combination of two or more kinds.

From the viewpoint of low water absorption without deteriorating the life of the electronic device, and from the viewpoint that the processing temperature can be easily controlled by changing the copolymerization ratio, the polymer is selected from aromatic vinyl compounds-conjugated diene copolymers and hydrogenation. One or more aromatic vinyl conjugate-diene copolymers are preferred.

The aromatic vinyl compound-conjugated diene copolymer is preferably an aromatic vinyl compound-conjugated diene block copolymer. The aromatic vinyl compound-conjugated diene block copolymer is selected from the group consisting of styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, and styrene-isoprene. One or more of a block copolymer and a styrene-isoprene-styrene block copolymer are preferred.

As the aforementioned hydrogenated aromatic vinyl compound-conjugated diene copolymer, a hydrogenated aromatic vinyl compound-conjugated diene block copolymer is preferred. The hydrogenated aromatic vinyl compound-conjugated diene block copolymer is selected from hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated benzene. One or more of ethylene-isoprene block copolymer and hydrogenated styrene-isoprene-styrene block copolymer are preferred. As more specific examples of these, Japanese Patent Publication No. H2-133406, Japanese Patent Publication No. H2-305814, Japanese Patent Publication No. H3-72512, Japanese Patent Publication No. 3-74409, and International Publication No. WO2015 / 099079 and other prior art documents.

As a hydrogenated aromatic vinyl compound-conjugated diene block copolymer, a hydrogenated aromatic vinyl compound-conjugated diene block copolymer that hydrogenates both unsaturated bonds of conjugated diene and aromatic ring Better.

A hydrogenated aromatic vinyl compound-conjugated diene block copolymer (also known as a "hydride") is a carbon-carbon of the main chain and side chain of an aromatic vinyl compound-conjugated diene block copolymer. Unsaturated bond and carbon-hydrocarbon obtained from aromatic ring. The hydrogenation rate is usually 90% or more, preferably 97% or more, and more preferably 99% or more. The higher the hydrogenation rate, the better the heat resistance and light resistance of the thermoplastic elastomer can be made. Here, the hydrogenation rate of the hydride can be determined by measurement by ¹ H-NMR.

In addition, the hydrogenation rate of the carbon-carbon unsaturated bond of the main chain and side chain of the aforementioned block copolymer is preferably 95% or more, and more preferably 99% or more. By increasing the hydrogenation rate of the carbon-carbon unsaturated bond of the main chain and side chain of the block copolymer, the light resistance and oxidation resistance of the resin can be further improved. In addition, the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring of the aforementioned block copolymer is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more. By increasing the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring, since the glass transition temperature of the hydride becomes higher, the heat resistance of the resin can be effectively improved. Furthermore, it is possible to reduce the photoelastic modulus of the resin, for example, to reduce the delay in discovery when used as a bonding layer.

Hydrogenated aromatic vinyl compound-a particularly preferred block form of a conjugated diene block copolymer, which is a block [A] of an aromatic ethylene polymer hydride bonded to the conjugated diene polymer hydride. Triblock copolymer at both ends of segment [B]; polymer block [B] is bonded to both ends of polymer block [A], and polymer block [A] is respectively bonded to the two Pentablock copolymer at the other end of the polymer block [B]. In particular, a triblock copolymer of [A]-[B]-[A] is particularly preferred because it is easy to manufacture and the physical properties of the thermoplastic elastomer can be set within a desired range.

In the hydrogenated aromatic vinyl compound-conjugated diene block copolymer, the total polymer block [A] accounts for the weight fraction wA of the entire block copolymer and the full polymer block [B] accounts for the block copolymerization. The ratio of the weight fraction wB (wA / wB) of the whole product is usually 20/80 or more, preferably 30/70 or more, and usually 60/40 or less, and 55/45 or less. By setting the aforementioned ratio wA / wB to be not less than the lower limit of the aforementioned range, the heat resistance of the resin can be improved. In addition, by setting the upper limit value or less, the flexibility of the resin can be improved, and the barrier properties of the resin can be stably maintained. Furthermore, since the sealing temperature can be reduced by lowering the glass transition temperature of the block copolymer, when the resin film of the present invention is applied to an organic EL device, an organic semiconductor device, or the like, thermal degradation of the device can be suppressed. Moreover, by setting the aforementioned ratio (wA / wB) within the aforementioned range, the temperature range in which the resin film has rubber elasticity can be widened, and the temperature range in which the electronic device has flexibility is widened.

[Polymer with polar group]

In the present invention, the resin preferably contains a polymer having a polar group as a polymer. When the resin contains a polymer having a polar group, the adhesion between the resin film and the device can be improved. Examples of such a polar group include a carbonyl group-containing or epoxy group such as an alkoxysilyl group, a carboxyl group, and an acid anhydride group, an amine group, and an isocyanate group. Among these, an alkoxysilyl group is preferable from the viewpoint of good bonding with inorganic substances, especially with Si-containing inorganic substances such as glass or SiOx.

The polymer having a polar group is preferably a graft polymer containing a polar group-containing unit. The polar group-containing unit refers to a unit having a structure obtained by polymerizing a monomer having a polar group. However, the unit containing a polar group is not limited depending on the manufacturing method.

A graft polymer containing a polar group-containing unit can be obtained by graft-polymerizing a polar group-containing monomer to a polymer. Hereinafter, in order to distinguish it from the polymer contained in the resin of the resin film of the present invention, the polymer supplied for the graft polymerization reaction is referred to as a "pre-reaction polymer". Examples of the pre-reaction polymer include the same polymers as those exemplified above as the polymer used as the main component of the resin.

Examples of the monomer having a polar group include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and dimethoxymethyl. Vinylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-propene Ethylene unsaturated silane compounds having an alkoxysilyl group, such as ethoxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, and 2-normen-5-yltrimethoxysilane.

By reacting the polymer before reaction with a monomer having a polar group, a polar group can be introduced into the polymer before the reaction, and a graft polymer containing a unit containing a polar group can be obtained. When an alkoxysilyl group is introduced as a polar group, the amount of the alkoxysilyl group introduced is usually 0.1 parts by weight or more, preferably 0.2 parts by weight or more, and 0.3 parts by weight based on 100 parts by weight of the polymer before the reaction. The above is preferred, and is usually 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 3 parts by weight or less. When the introduction amount of the alkoxysilyl group is within the aforementioned range, the degree of cross-linking of the alkoxysilyl groups which are decomposed by moisture or the like can be prevented from being excessively high, and thus high bonding properties can be maintained. Examples of the alkoxysilyl group-containing substance and the modification method used for the introduction of the alkoxysilyl group include those described in prior art documents such as International Publication No. WO2015 / 099079.

The amount of introduced alkoxysilyl group can be measured by ¹ H-NMR spectrum. In addition, when measuring the introduction amount of alkoxysilyl group, if the introduction amount is small, it is necessary to increase the number of accumulations to measure.

"Introducing the alkoxysilyl group before the reaction as a polar group" is called silane modification. When the silane is modified, the alkoxysilyl group can be directly bonded to the polymer before the reaction, or it can be bonded through a divalent organic group such as an alkylene group. Hereinafter, the polymer obtained by the silane modification of the polymer before the reaction is also referred to as "silane modified polymer".

In the present invention, as the silane-modified polymer, a silane-modified product selected from a hydrogenated styrene-butadiene block copolymer, a silane-modified product of a hydrogenated styrene-butadiene-styrene block copolymer, One or more silane modified products of hydrogenated styrene-isoprene block copolymer and silane modified products of hydrogenated styrene-isoprene-styrene block copolymer are preferable.

The weight average molecular weight (Mw) of the silane-modified polymer is usually more than 20,000, preferably more than 30,000, more preferably 35,000 or more, and usually less than 200,000, preferably less than 100,000, and preferably less than 70,000. The weight average molecular weight of the polymer was measured by gel permeation chromatography using tetrahydrofuran as a solvent, and the value was measured in terms of styrene conversion. The molecular weight distribution (Mw / Mn) of the polymer is preferably 4 or less, more preferably 3 or less, particularly preferably 2 or less, and more preferably 1 or more. By concentrating the polymer's weight average molecular weight Mw and molecular weight distribution Mw / Mn within the aforementioned ranges, the mechanical strength and heat resistance of the resin can be improved.

Silane-modified polymers have excellent adhesion to materials such as glass, inorganics, and metals. Therefore, when the element of the organic EL light-emitting device is sealed by the resin film of the present invention, the adhesion between the resin film and the element can be particularly improved. Therefore, after long-term exposure to high-temperature and high-humidity environments usually performed for reliability evaluation of organic EL light-emitting devices, the resin film can maintain sufficient bonding power.

[2.2. Hygroscopic particles]

The primary particle diameter of the hygroscopic particles dispersed in the resin is 200 nm or less. By setting the primary particle diameter of the hygroscopic particles to 200 nm or less, the thickness of the resin film can be made uniform. The primary particle diameter of the hygroscopic particles is preferably 150 nm or less, and more preferably 100 nm or less. By reducing the primary particle size of the hygroscopic particles, the internal haze value can be reduced, and the transparency of the resin film can be improved.

The primary particle size of the hygroscopic particles is preferably 3 nm or more, and more preferably 10 nm or more. With the primary particle diameter of the hygroscopic particles being above the aforementioned lower limit value, the particles can be dispersed with a small dispersing amount, and the adverse effects caused by the dispersant can be reduced, and the hygroscopicity can be improved. In the present invention, the primary particle size means the number average particle size of the primary particles. The primary particle diameter (number-average particle diameter) of the hygroscopic particles can be measured by a particle size measuring device using a dynamic light scattering method in a state of being dispersed in a solvent dispersion. Further, as another method, particles in the resin cross section can be directly observed with an electron microscope in a resin state, and measured by means of obtaining an average value of the particle diameter.

In the present invention, the so-called hygroscopic particles are particles whose weight changes are confined in a specific range when left at 20 ° C and 90% RH for 24 hours. The specific range of the weight change rate is usually 3% or more, preferably 10% or more, and more preferably 15% or more. The upper limit of the weight change rate is not particularly limited, but is preferably 100% or less. By using such hygroscopic particles with high hygroscopicity, it is possible to sufficiently absorb moisture in a small amount, so when the resin is a thermoplastic elastomer, the rubber characteristics originally possessed by the thermoplastic elastomer are not hindered, which is advantageous. .

The weight change rate can be calculated according to the following formula (A1). In the following formula (A1), W1 represents the weight of the particles before being left in an environment of 90% Rh at 20 ° C, and W2 represents the weight of the particles after being left in an environment of 90% Rh at 20 ° C. Weight change rate (%) = (W2−W1) / W1 × 100 (A1)

Examples of the material contained in the hygroscopic particles include alkali metals, alkaline earth metals, aluminum-containing compounds (oxides, hydroxides, salts, etc.) without silicon-containing compounds (such as barium oxide, magnesium oxide, and oxides). Calcium, strontium oxide, aluminum hydroxide, hydrotalcite, etc.), organometallic compounds described in Japanese Patent Publication No. 2005-298598, and alkaline hygroscopic agents such as clay containing metal oxides; inorganic compounds containing silicon (for example, Silica gel, nanoporous silica, zeolite) and other acidic hygroscopic agents.

As the material of the hygroscopic particles, one or more materials selected from the group consisting of zeolite and hydrotalcite are preferable. Zeolite especially has high hygroscopicity. For example, when it is left at 20 ° C and 90% RH for 24 hours, it can easily achieve a high weight change rate of 10% to 30%. Furthermore, since zeolite releases water due to drying, it can be reused. As the material for the moisture-absorbing particles described above, one kind may be used alone, or two or more kinds may be used in combination at any ratio.

In the present invention, the absolute value of the difference between the refractive index of the resin and the refractive index of the hygroscopic particles is 0.05 or less. By setting the absolute value of the difference between the refractive indices of the resin and the hygroscopic particles to the aforementioned range, it is possible to reduce the internal haze and improve the transparency of the resin film. The absolute value of the difference between the refractive index of the resin and the refractive index of the hygroscopic particles is preferably 0.03 or less.

The refractive index of the hygroscopic particles can be measured by the standard solution method. Specifically, 2 to 3 standard reagents having a known refractive index are dropped onto a glass substrate, and hygroscopic particles are mixed therein to prepare a mixed solution. This operation is performed using a standard solution reagent (CARGILLE standard refractive index liquid manufactured by MORITEX Corporation) having various refractive indexes, and the refractive index of the standard solution reagent when the aforementioned mixed solution becomes transparent is taken as the refractive index of each particle. On the other hand, the refractive index of the resin is set to a refractive index at a wavelength of 589 nm measured by an Abbe refractometer or a spectroscopic ellipsometry, if it has been formed into a thin film.

The amount of hygroscopic particles in the resin is preferably 5% by weight or more, more preferably 10% by weight or more, more preferably 60% by weight or less, preferably 40% by weight or less, and 30% by weight or less. Better. When the amount of the moisture-absorbing particles is equal to or more than the lower limit value of the aforementioned range, the effect of preventing moisture penetration of the resin film can be improved. In addition, the transparency, softness, and processability of the resin film can be improved by being below the upper limit of the above range.

[2.3. Dispersant]

In the present invention, the resin film contains a dispersant. The dispersant plays a role in improving the dispersibility of the hygroscopic particles in the resin. Examples of dispersants include the "Aron (registered trademark)" and "JURYMER (registered trademark)" series of Toa Kosei Corporation, the "AQUALIC (registered trademark)" series of Japan Catalyst Corporation, and the Kyoeisha Chemical Co., Ltd. "FLOWLEN (registered trademark)" series, "DISPARLON (registered trademark)" series of Kusumoto Chemical Co., Ltd., "Sokalan (registered trademark)" series of BASF company, "DISPERBYK (registered trademark)" series of BYK company, Japan's Lubrizol company Commercially available dispersants such as the "SOLSPERSE (registered trademark)" series and the "AJISPER" series of Ajinomoto Fine-Techno. The dispersant can be made of a skeleton adsorbed on the hygroscopic particles and a skeleton that affects the interaction or compatibility with the resin or solvent.

Examples of the skeleton adsorbed on the hygroscopic particles include an amine group, a carboxyl group, a phosphate group, an amine salt, a carboxylate, a phosphate, an ether group, a hydroxyl group, a sulfonylamino group, an aromatic vinyl group, and an alkyl group. When the hygroscopic particles are acidic hygroscopic particles, it is preferable to use an alkaline (basic dispersant) as the adsorption skeleton. When the hygroscopic particles are alkaline hygroscopic particles, use an acidic (an acidic dispersant) ) Is good as an adsorption framework, but it can also be a nonionic dispersant.

The lower limit of the acid value or the base value (amine value) of the dispersant is preferably 20 mg KOH / g or more, and more preferably 50 mg KOH / g or more. The upper limit of the acid value or base value is preferably 200 mg KOH / g or less, and more preferably 160 mg KOH / g or less. By selecting a dispersant having an acid value or a basic value (amine value) within this range, the particles can be efficiently dispersed in a short time. On the other hand, examples of a skeleton that affects the interaction or compatibility with a resin or a solvent include fatty acids, polyamines, polyethers, polyesters, polyurethanes, and polyacrylates. Moreover, the dispersant selected is preferably soluble in non-polar solvents. Non-polar solvents generally contain less water in the solvent and do not hinder the performance of the hygroscopic particles. Examples of such a non-polar solvent include hexane, cyclohexane, toluene, benzene, tetrahydrofuran, and the like.

In addition, a silane coupling agent such as Shin-Etsu Silicone Co., Ltd. or Dow Corning Toray Co., Ltd. may be used as a dispersant. In the case of a silane coupling agent, the part adsorbed on the hygroscopic particles is called a hydrolyzable group, and the part that affects the interaction or compatibility with a resin or a solvent is called a reactive functional group. For example, examples of the hydrolyzable group include -OCH ₃ , -OC ₂ H ₅ , -OCOCH ₃ and the like. On the other hand, examples of the reactive functional group include an amino group, an epoxy group, a methacryl group, and a vinyl group. These dispersants can be used singly or in combination.

The amount of the dispersant is preferably 7 parts by weight or more, more preferably 10 parts by weight or more, more preferably 70 parts by weight or less, and 50 parts by weight or less with respect to 100 parts by weight of the hygroscopic particles. By setting the amount of the dispersant to be equal to or more than the aforementioned lower limit value, good dispersion of the moisture-absorbing particles can be achieved, and the internal haze can be reduced to achieve high transparency. By setting the amount of the dispersant to be equal to or less than the aforementioned upper limit value, it is possible to suppress a decrease in adhesion between the resin film and the organic EL light-emitting device and the like caused by the dispersant.

[2.4. Arbitrary ingredients]

The resin must contain any component other than the polymer. Examples of arbitrary components include plasticizers for adjusting glass transition temperature and elastic modulus, light stabilizers for improving weather resistance and heat resistance, ultraviolet absorbers, antioxidants, lubricants, and inorganic fillers. Wait. In addition, an arbitrary component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

Examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, and the like, and phosphorus-based antioxidants with less coloration are preferred.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl phosphite isodecyl, phenyl phosphite diisodecyl, phosphite (nonylphenyl), and phosphite (dinonyl). ) Ester, phosphite [2,4-bis (tertiary butyl) phenyl] ester, 10 [3,5-bis (tertiary butyl) -4-hydroxybenzyl] -9,10-dihydro- Monophosphite compounds such as 9-oxy-10-phosphinophenanthrene-10-oxide; 4,4'-butylene bis (3-methyl-6-tert-butylphenyl bis (tridecyl) phosphite Ester), 4,4'-isopropylidene bis (phenylbis (alkyl (C12 to C15) phosphite)) and other diphosphite-based compounds; 6- [3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetrakis (tributyl) diphenyl [d, f] [1.3.2] dioxophosphonium, 6- { 3- [3,5-bis (tertiary-butyl) -4-hydroxyphenyl] propoxy} -2,4,8,10-tetrakis (tertiary-butyl) diphenyl [d, f] [1.3 .2] Compounds such as dioxin.

Examples of the phenol-based antioxidant include tetra {3- [3,5-bis (tertiarybutyl) -4-hydroxy] propanoic acid} neopentaerythritol, and 2,2′-thiodiethylene ethylbis [3- (3,5-bis (tertiarybutyl) -4-hydroxyphenyl) propionate], 3- [3,5-bis (tertiarybutyl) -4-hydroxyphenyl] propionic acid Octadecyl ester, 3,9-bis {2- [3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propanyloxy] -1,1-dimethylethyl} -2,4,8,10-Tetraspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-ginseng [3,5-bis (tertiary butyl) Compounds such as 4-hydroxybenzyl] benzene.

Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-dipropionate, and distearyl 3,3'-dipropionate , 3,3'-Lauryl thiodipropionate stearyl ester, β-laurylthiopropionate neopentyl tetraester, 3,9-bis (dodecylthioethyl) -2,4, 8,10-tetraoxo [5,5] undecane and other compounds.

The amount of the antioxidant is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and usually 1 part by weight or less, based on 100 parts by weight of the main component polymer. The content is preferably less than or equal to 0.3 parts by weight. The use of an antioxidant having a lower limit value or more in the aforementioned range can improve the durability of the resin film, but even if it is used in excess of the upper limit, it is difficult to obtain further improvement.

[3. Composition of resin film]

An arbitrary layer may be provided on one side surface or both sides of the resin film of the present invention according to storage, transportation, use, and the like. Examples of the arbitrary layer include a release film. Specifically, a resin film and a release film can be laminated to form a laminate. When a resin film is used as a bonding film, it is suitable that the resin film can be easily stored and transported in the state of a laminate. Examples of the release film include a film made of polyethylene terephthalate (PET) that has been subjected to a release treatment.

The thickness of the resin film of the present invention is preferably 0.1 μm or more, more preferably 1 μm or more, more preferably 3 μm or more, particularly preferably 5 μm or more, and more preferably 1000 μm or less, and more preferably 100 μm or less. It is more preferably 50 μm or less, and particularly preferably 16 μm or less. By setting the thickness of the resin film to be greater than or equal to the aforementioned lower limit, effective moisture absorption can be easily achieved, and thereby, intrusion of moisture can be easily achieved. By setting the thickness of the resin film to the aforementioned upper limit value or less, the flexibility of the resin film of the present invention can be made good.

The storage elastic modulus of the resin film of the present invention at 25 ° C is preferably 10 ⁷ Pa or more, more preferably 2 × 10 ⁷ Pa or more, and preferably 10 ⁹ Pa or less, and 5 × 10 ⁸ Pa or less. Better. By setting the storage elastic modulus of the resin film at 25 ° C within the aforementioned range, the resin film can be made into a structure having rubber elasticity even in a normal use temperature environment. A suitable one is a flexible device.

The storage elastic modulus of the resin film at 25 ° C can be measured using a dynamic viscoelasticity measuring device at a frequency of 1 Hz.

The internal haze of the resin film of the present invention is preferably 6.0% or less, more preferably 3.0% or less, and even more preferably 1.0% or less. By making the internal haze below the above range, since the transparency of the resin film is improved, the resin film can be suitably used in places where light transmission is required in organic EL light-emitting devices and the like. The internal haze was measured by using a turbidimeter.

The glass transition temperature of the resin constituting the resin film is not particularly limited, but it is preferably 40 ° C or higher, more preferably 70 ° C or higher, and usually 200 ° C or lower, preferably 180 ° C or lower, and 160 ° C or lower. good. In addition, for example, when a thermoplastic elastomer containing a block copolymer is used, the glass transition temperature can be adjusted by changing the weight ratio of each polymer block to obtain the bonding property at the time of sealing and the flexibility after sealing. Of balance.

The manufacturing method of the resin film of this invention is not specifically limited, It can be manufactured by arbitrary methods. For example, a mixture obtained by mixing the components (polymer, hygroscopic particles, dispersant, and other components added as needed) constituting the resin film can be applied to a PET film that has been subjected to a release treatment, etc. The substrate is manufactured by drying the substrate. The method of mixing the components constituting the resin film is not particularly limited, and examples thereof include the use of a kneader such as a biaxial kneader, a roll, a Brabender, and an extruder to bring the polymer into a molten state. A method of kneading with components other than the polymer; a method of dissolving or dispersing components other than the polymer in an appropriate solvent and mixing the solution with the polymer; removing the solvent to recover a resin containing other components; and the like.

[4. Use of resin film]

The resin film of the present invention is used in electronic devices, and is used for supporting substrates, insulation, bonding, and sealing. Among these uses, for example, in the case of use as a bonding application (bonding layer), the resin film of the present invention is interposed between two layers to be bonded, and a treatment for developing bonding properties is applied to thereby The two layers to be joined in this way must be joined.

The process for expressing the bonding property is specifically a so-called hot-melt process. That is, the resin film of the present invention is heated, and if necessary, a process of applying pressure between the two layers to be joined is performed. The treatment temperature is preferably performed at a temperature of Tg or higher, and more preferably performed at a temperature of Tg + 50 ° C or higher. Here, Tg means the glass transition temperature of the resin constituting the resin film. In the case where the resin has a plurality of glass transition temperatures, the aforementioned Tg indicates the highest glass transition temperature among them. As a result, a good joint can be achieved. The upper limit of the processing temperature is preferably Tg + 50 ° C or lower, and more preferably Tg + 30 ° C or lower. By processing at a temperature below the upper limit, the transfer of the hygroscopic particles and the dispersant to the outermost surface of the resin film can be effectively suppressed. As a result, the chemical reaction between the hygroscopic particles and the layer to be bonded can be suppressed, and Suppress physical adverse effects caused by secondary particles of hygroscopic particles.

[5. Electronic devices]

The electronic device of the present invention includes the resin film for an electronic device of the present invention. Examples of such electronic devices include organic EL light-emitting devices, solar cells, touch panels, and various electrodes (ITO, copper electrodes, tin electrodes, solder electrodes, etc.). Among these, an organic EL light-emitting device including the resin film of the present invention as a sealing film is preferred. By using the resin film of the present invention as a sealing film, it is obtained in an organic EL light-emitting device that is easily affected by moisture or oxygen, and effectively exhibits an effect of preventing moisture from entering. The organic EL light-emitting device provided with the resin film of the present invention will be described below as a specific example of the electronic device of the present invention.

The organic EL light-emitting device may include a substrate, an electrode and a light-emitting layer provided thereon. Specifically, a substrate including a glass plate, a first electrode provided on the surface, a light-emitting layer provided on the surface, and a second electrode provided on the surface can be obtained. By setting one of the first electrode and the second electrode as a transparent electrode, and setting the other as a reflective electrode (or a combination of a transparent electrode and a reflective layer), it is possible to achieve access by responding to the energization of the electrode. Light emission on the transparent electrode side.

The organic EL light-emitting device may further include a gas barrier layer for preventing moisture from entering the inside of the light-emitting layer. The organic EL light-emitting device may include a substrate, a gas barrier layer, an electrode and a light-emitting layer provided therebetween, and a structure in which the electrode and the light-emitting layer are sealed by the substrate and the gas-barrier layer. An organic EL light-emitting device may include the resin film of the present invention as a layer interposed between a second electrode and a gas barrier layer. If such a structure is adopted and the resin film of the present invention functions as a bonding layer that joins the second electrode and the gas barrier layer, it is possible to obtain a layer that prevents moisture from entering the light-emitting layer and the like with high adhesiveness, thereby effectively emitting the light. An organic EL light-emitting device sealed in layers.

The gas barrier layer provided in the organic EL light-emitting device can be made into a stacked body of a resin film and a gas barrier layer. For example, a gas barrier stack including a resin film and an inorganic barrier layer formed on a surface thereof may be used as the gas barrier layer.

Preferred examples of the inorganic material included in the inorganic barrier layer include metals; oxides, nitrides, and oxynitrides of silicon; oxides, nitrides, and oxynitrides of aluminum; and DLC (Diamond-Like Carbon) ; And a mixture of two or more of these materials; etc. Among them, in terms of transparency, a material containing silicon is preferable, and silicon oxide and silicon nitrogen oxide are particularly preferable. Further, in terms of the affinity with the resin film, DLC is particularly preferred.

Examples of the silicon oxide include SiO _x . Here, from the viewpoint of considering both the transparency of the inorganic barrier layer and the water vapor barrier property, x is preferably 1.4 <x <2.0. In addition, as an oxide of silicon, SiOC may be mentioned.

Examples of silicon nitride include SiN _y . Here, from the viewpoint of considering both the transparency of the inorganic barrier layer and the water vapor barrier property, y is preferably 0.5 <y <1.5.

Examples of silicon oxynitride include SiO _p N _q . Here, in the case where the improvement of the adhesion of the inorganic barrier layer is important, it is preferable that the film is set to 1 <p <2.0 and 0 <q <1.0, and the inorganic barrier layer is an oxygen-rich film. When the improvement of the water vapor barrier property of the inorganic barrier layer is important, it is preferable to set the inorganic barrier layer to an oxygen-enriched film with 0 <p <0.8 and 0.8 <q <1.3.

Examples of the oxides, nitrides, and oxynitrides of aluminum include AlO _x , AlN _y, and _Op N _q . Among them, from the viewpoint of inorganic barrier properties, a mixture of SiO _p N _q , AlO _x and the like is particularly preferred.

The inorganic barrier layer can be formed by, for example, a vapor deposition method, a sputtering method, an ion plating method, an ion beam assisted evaporation method, an arc discharge plasma evaporation method, a thermal CVD method, or a plasma CVD method. The surface of the resin film of the support. Among them, a chemical vapor deposition method such as a thermal CVD method or a plasma CVD method is preferably used. According to the chemical vapor deposition method, a flexible inorganic barrier layer can be formed by adjusting the gas composition used for film formation. In addition, by obtaining a flexible inorganic barrier layer, the inorganic barrier layer can follow the deformation of the resin film and the size change of the resin film under a high temperature and high humidity environment. In addition, according to the chemical vapor deposition method, a film can be formed at a high film formation rate in an environment with a low degree of vacuum, and good gas barrier properties can be achieved.

In the gas barrier stack, although the inorganic barrier layer may be provided on both sides of the resin film, it is usually provided on one side. At this time, the inorganic barrier layer may be disposed to face the inside of the organic EL light emitting device, or may be disposed to face the outside of the organic EL light emitting device. From the viewpoint of preventing damage to the inorganic barrier layer after the device is manufactured, it is preferable to be provided to face the inside of the organic EL light-emitting device.

The organic EL light-emitting device may further include an arbitrary layer such as a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer between the first electrode and the second electrode. The organic EL light-emitting device may have any structure such as a wiring for energizing the first electrode and the second electrode, and a peripheral structure for sealing the light-emitting layer.

The organic EL light-emitting device may include a light-emitting layer in any form. For example, the electronic device of the present invention may be a display device having a light emitting layer as a pixel for displaying an image, or a light source device such as a backlight device or a lighting device having a light emitting layer as a light source for supplying light.

The following examples are disclosed to illustrate the present invention in detail. However, the present invention is not limited to the embodiments disclosed below, and can be implemented with arbitrary changes without departing from the scope of the patent application of the present invention and its equivalent scope. In the following description, unless otherwise noted, "%" and "parts" indicating the weight are based on weight. In addition, the operations described below are performed under normal temperature and pressure conditions unless otherwise noted.

[Evaluation method]

[Young's modulus, tensile elongation, and tan δ of the resin]

The Young's modulus and tensile elongation of the resin at 23 ° C are measured in accordance with JIS K7113. The loss tangent tanδ (loss modulus / storage modulus) of the resin above 40 ° C and below 200 ° C is measured using a dynamic viscoelasticity measuring device DMS6100 manufactured by Hitachi Advanced Technologies.

[Refractive index]

The refractive index of the hygroscopic particles is measured by a standard solution method. Specifically, 2 to 3 standard reagents having a known refractive index are dropped onto a glass substrate, and hygroscopic particles are mixed therein to prepare a mixed solution. This operation is performed using a standard solution reagent (CARGILLE standard refractive index liquid manufactured by MORITEX Corporation) having various refractive indexes, and the refractive index of the standard solution reagent when the aforementioned mixed solution becomes transparent is taken as the refractive index of each particle. On the other hand, the refractive index of the resin is prepared by forming it into a thin film, and it is measured with an Abbe refractometer at a wavelength of 589 nm.

[Measurement method of Ca film corrosion onset time]

A 5 cm square glass substrate 1 and a 4 cm square glass substrate 2 on which a Ca film is formed are formed in a square-shaped area having a side length of 3 cm. Then, the multilayer film produced in the examples and comparative examples was peeled and released from the PET film to obtain a resin film 1. This was cut into a square having a side length of about 4.0 cm to obtain a resin film 1 as a sample.

The resin film 1 is placed on the glass substrate 1, and then, the glass substrate 2 is placed on the resin film 1 so that the end of the Ca film region comes to a distance of 0.5 cm from the end of the glass substrate 2. By passing it through a roll bonding machine with a roller temperature set to 110 ° C. under a pressure of 0.3 MPa to bond them, a glass substrate having (glass substrate 2) / (resin film 1) / (glass substrate 1) was produced. Layered glass stack 1. The obtained glass stack 1 was stored in an environment of 60 ° C and 90% RH, and the presence or absence of discoloration at the ends of the Ca film region was observed every 24 hours, and the start time of discoloration at the ends of the Ca film region was measured. The longer the discoloration start time at the end of the Ca film region, the better the moisture permeability of the resin film.

[Measurement method of internal haze]

A 5 cm square glass substrate 3 and a 5 cm square glass substrate 4 were prepared. Then, the multilayer film produced in the examples and comparative examples was peeled and released from the PET film to obtain a resin film 1.

A resin film 1 is disposed on the glass substrate 3. A glass substrate 4 was further placed thereon and passed through a roll bonding machine with a roller temperature set to 110 ° C. under a pressure of 0.3 MPa to bond them together to produce (glass substrate 3) / (resin film). 1) / (glass substrate 4) A glass stack 2 composed of layers. The haze of the obtained glass laminate 2 was measured using a haze meter ("NDH-2000" manufactured by Nippon Denshoku Co., Ltd.).

[Measurement method of storage elastic modulus of resin film]

The multilayer PET films produced in the examples and comparative examples were peeled and released from the PET film to obtain a resin film. For the resin film, a dynamic viscoelasticity measuring device DMS6100 manufactured by Hitachi Advanced Technologies was used to measure a storage elastic modulus of −50 ° C to 200 ° C at a frequency of 1 Hz. The storage elastic modulus at 25 ° C is shown in the table.

[Adhesion evaluation test (checkerboard peel test)]

A 5 cm square glass substrate 5 and the multilayers produced in the examples and comparative examples were prepared.

On a 5 cm square glass substrate 5, a multilayer was disposed such that the release-treated PET film was on the upper side, and passed through a roller bonding machine with a roller temperature set to 110 ° C. under a pressure of 0.3 MPa to bond them together. , And then stored in an oven at 80 ℃ for 1 hour. In this way, a glass laminate 3 having a layer structure of (release film PET film) / (film resin film 1) / (glass substrate 5) was produced. From then on, the glass laminate 3 was only peeled from the release-treated PET film, and a resin knife was used to cut 11 vertical and horizontal cuts at 1 mm intervals to make 100 (10 × 10) 1 mm square checkers. Here The cellophane tape was affixed thereon and quickly peeled off, and the number of checkerboard cells remaining without peeling was evaluated by the following evaluation criteria. The larger the number of checkerboard cells that remain without peeling, the better the adhesion to the glass substrate.

<Evaluation Criteria> OK: The number of checkerboards remaining without peeling off from the total checkerboard number (100) is 90 or more. NG: The number of checkerboards remaining without peeling off from the full checkerboard partition (100) is 89 or less.

[Example 1]

(1-1. Manufacture of hydrogenated block copolymer)

Using styrene as the aromatic vinyl compound and isoprene as the chain conjugated diene compound, a polymer block [A] having a polymer block [B] bonded to both ends thereof was produced in the following procedure: Triblock structure hydrogenated block copolymer (hydrogenated block copolymer).

In a reactor equipped with a stirring device that has been sufficiently replaced with nitrogen, 256 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene and 0.615 parts of di-n-butyl ether are added, and n-butyllithium ( 15% cyclohexane solution) 1.35 parts to start polymerization, and the mixture was allowed to react at 60 ° C for 60 minutes while stirring. The polymerization conversion rate at this time point was 99.5% (the polymerization conversion rate was measured by gas chromatography. The same applies hereinafter).

Next, 50.0 parts of dehydrated isoprene was added, and stirring was continued for 30 minutes at the same temperature. The polymerization conversion rate at this time point was 99%.

After that, 25.0 parts of dehydrated styrene was further added and stirred at the same temperature for 60 minutes. The polymerization conversion at this time point was almost 100%.

Subsequently, 0.5 part of isopropyl alcohol was added to the reaction solution to stop the reaction, and a solution (i) containing a block copolymer was obtained.

The weight average molecular weight (Mw) of the block copolymer in the obtained solution (i) was 44,900, and the molecular weight distribution (Mw / Mn) was 1.03.

Next, move the solution (i) to a pressure-resistant reactor equipped with a stirring device, and add 4.0 parts of silicon-aluminum-supported nickel catalyst (E22U, nickel loading 60%; manufactured by Niwa Chemical Industry Co., Ltd.) to the solution (i) and 350 parts of dehydrated cyclohexane was used as a hydrogenation catalyst and mixed. The inside of the reactor was replaced with hydrogen, and then hydrogen was supplied while stirring the solution, and the block copolymer was hydrogenated by performing a hydrogenation reaction at a temperature of 170 ° C and a pressure of 4.5 MPa for 6 hours to obtain a hydride containing the block copolymer (ii ) Solution (iii). The weight average molecular weight (Mw) of the hydride (ii) in the solution (iii) was 45,100, and the molecular weight distribution (Mw / Mn) was 1.04.

After the hydrogenation reaction is completed, the solution (iii) is filtered to remove the hydrogenation catalyst. After that, 6- [3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8, in which the filtered solution (iii) had been dissolved, was added. 10- (tri-butyl) diphenyl [d, f] [1.3.2] dioxophosphonium ("SUMILIZER (registered trademark) GP" manufactured by Sumitomo Chemical Co., Ltd. hereinafter referred to as "antioxidant A") 0.1 Part (x) of the xylene solution was dissolved as a phosphorus-based antioxidant to obtain a solution (iv).

Subsequently, the solution (iv) was filtered using a Zeta Plus (registered trademark) filter 30H (manufactured by CUNO, pore size 0.5 μm to 1 μm), and then filtered using other metal fiber filters (pore size 0.4 μm, manufactured by NICHIDAI) in order. Removes tiny solids. Cyclohexane, xylene, and other volatiles were removed from the filtered solution (iv) using a cylindrical concentrator dryer (brand name "KONTRO", manufactured by Hitachi, Ltd.) at a temperature of 260 ° C and a pressure of 0.001 MPa or less ingredient. Then, from a mold directly connected to the above-mentioned concentration dryer, the solid component was extruded into a strand shape in a molten state and cooled, and cut with a pelletizer to obtain 85 parts of pellets containing a block copolymer hydride and an antioxidant ( v). The weight average molecular weight (Mw) of the hydrogenated product (hydrogenated block copolymer) of the block copolymer in the obtained particles (v) was 45,000, and the molecular weight distribution (Mw / Mn) was 1.08. The hydrogenation rate was 99.9%.

(1-2. Manufacture of Silane Modified Hydrogenated Block Copolymer)

With respect to 100 parts of the particles (v) obtained in (1-1), 2.0 parts of vinyltrimethoxysilane and 0.2 part of bis (tertiarybutyl) peroxide were added to obtain a mixture. This mixture was kneaded with a biaxial extruder at a barrel temperature of 210 ° C and a residence time of 80 seconds to 90 seconds. The kneaded mixture is extruded and cut with a granulator to obtain particles (vi) of a silane modified product of a hydrogenated block copolymer. A film-like test piece was produced from the particles (vi), and the glass-glass transition temperature Tg of the tan δ peak value of the dynamic viscoelasticity measuring device was 124 ° C. The peak of tan δ of the particles (vi) above 40 ° C and below 200 ° C is 1.3. The 23 ° C Young's modulus of the particles (vi) was 0.5 GPa and the tensile elongation was 550%. In addition, the refractive index (n1) of this particle (vi) measured by an Abbe refractometer is 1.50.

(1-3. Production of resin film)

A bead mill was used to mix 10 g of zeolite particles (the number of primary particles in a dispersed state, an average particle diameter of 50 nm, and a refractive index (n2) of 1.5). -109 ", manufactured by BYK Co., the same below) 5 g and 185 g of cyclohexane to prepare a 5% zeolite dispersion 1. Next, 40 g of particles (vi) obtained in (1-2) and 160 g of cyclohexane were mixed, and the particles were dissolved to prepare a 20% polymer solution.

The zeolite dispersion liquid 1 and the polymer solution were weighed in equal amounts and mixed to prepare a zeolite-containing polymer solution. Using a device, apply a polymer solution containing zeolite to a release-treated PET film (a PET film that has been subjected to a release treatment on one side, trade name MRV38, manufactured by Mitsubishi Resin Co., Ltd., the same below) to 110 The solvent was evaporated by drying the heated plate at 3 ° C for 3 minutes. By this operation, a multilayered article including a release-treated PET film and a resin film formed thereon was obtained. The resin film in the multilayer contains 18.1% of zeolite and has a thickness of 10 μm. The multilayer material was stored in a nitrogen environment so that moisture absorption would not proceed, and the corrosion start time, internal haze, storage elastic modulus, and adhesion of the Ca film were evaluated in accordance with the evaluation method described above.

[Example 2]

Except having replaced the 5% zeolite dispersion 1 with the following 5% zeolite dispersion 2 in Example 1-3 (1-3), it carried out similarly to Example 1, and obtained and evaluated the multilayered object. The resin film in the multilayer contains 19.4% zeolite and has a thickness of 10 μm.

5% zeolite dispersion 2 is a zeolite particle mixed with a bead mill (the number of primary particles in the dispersed state, the average particle diameter is 190nm, the refractive index (n2) is 1.50), 10g, and the dispersant with an alkaline adsorption group is 1.5g. 188.5 g of cyclohexane was produced.

[Example 3]

Except that in Example 1 (1-3), the following 5% hydrotalcite dispersion 3 was used instead of the 5% zeolite dispersion 1, the same operation as in Example 1 was performed, and a multilayer product was obtained and evaluated. The resin film in the multilayer contains 19.6% hydrotalcite and has a thickness of 10 μm.

5% Hydrotalcite Dispersion Liquid 3 is a bead mill that mixes and mixes hydrotalcite particles (the number of primary particles in the dispersed state, the average particle size is 50 nm, the refractive index (n2) is 1.52), and a dispersant (acid with an acid adsorption group) The price is 101 mg KOH / g, trade name "DISPERBYK-102", manufactured by BYK Co., the same below) 1 g and 189 g of cyclohexane.

[Comparative Example 1]

(C1-1. Production of resin film)

A bead mill was used to mix and mix 10 g of magnesium oxide particles (the number of primary particles in a dispersed state, an average particle diameter of 50 nm, a refractive index (n2) of 2.00), 10 g of a dispersant having an alkaline adsorption group, and 180 g of cyclohexane to make 5%. Magnesium oxide dispersion C1. Next, 40 g of the particles (vi) obtained in (1-2) of Example 1 and 160 g of cyclohexane were mixed, and the particles were dissolved to prepare a 20% polymer solution.

The magnesium oxide dispersion C1 and the polymer solution were weighed at a ratio of 1: 2 and mixed to prepare a polymer solution containing magnesium oxide. Using a device, the polymer solution containing magnesium oxide was applied to a release-treated PET film, and dried on a hot plate at 110 ° C. for 3 minutes to evaporate the solvent. By this operation, a multilayered article including a release-treated PET film and a resin film formed thereon was obtained. The resin film in the multilayer contains 10% of magnesium oxide dispersed therein and has a thickness of 10 μm. The multilayer material was stored in a nitrogen environment so that moisture absorption would not proceed, and the corrosion start time, internal haze, storage elastic modulus, and adhesion of the Ca film were evaluated in accordance with the evaluation method described above.

[Comparative Example 2]

(C2-1. Production of resin film)

A bead mill was used to stir and mix hydrotalcite particles (the average number of primary particles in the dispersed state was 500 nm, the refractive index (n2) was 1.55), 10 g, 10 g of a dispersant having an acidic adsorbing group, and 180 g of cyclohexane to make 5% water. Talc dispersion liquid C2. Next, 40 g of the particles (vi) obtained in (1-2) of Example 1 and 160 g of cyclohexane were mixed, and the particles were dissolved to prepare a 20% polymer solution.

The hydrotalcite dispersion liquid C2 and the polymer solution were weighed at a ratio of 1: 2 and mixed to prepare a polymer solution containing hydrotalcite. Using a device, the polymer solution containing hydrotalcite was coated on a release-treated PET film, and dried on a hot plate at 110 ° C. for 3 minutes to volatilize the solvent. By this operation, a multilayered article including a release-treated PET film and a resin film formed thereon was obtained. The resin film in the multilayer contains 10% of hydrotalcite dispersed therein and has a thickness of 10 μm. The multilayer material was stored in a nitrogen environment so that moisture absorption would not proceed, and the corrosion start time, internal haze, storage elastic modulus, and adhesion of the Ca film were evaluated in accordance with the evaluation method described above.

[Comparative Example 3]

(C3-1. Production of resin film)

A bead mill was used to mix and mix 10 g of magnesium oxide particles (the number of primary particles in a dispersed state, an average particle diameter of 20 nm, a refractive index (n2) of 2.00), 10 g of a dispersant having an alkaline adsorption group, and 180 g of cyclohexane to make 5% Magnesium oxide dispersion C3. Next, 40 g of the particles (vi) obtained in (1-2) of Example 1 and 160 g of cyclohexane were mixed, and the particles were dissolved to prepare a 20% polymer solution.

The magnesium oxide dispersion C3 and the polymer solution were weighed at a ratio of 1: 2 and mixed to prepare a polymer solution containing magnesium oxide. Using a device, the polymer solution containing magnesium oxide was applied to a release-treated PET film, and dried on a hot plate at 110 ° C. for 3 minutes to evaporate the solvent. By this operation, a multilayered article including a release-treated PET film and a resin film formed thereon was obtained. The resin film in the multilayer contains 10% of magnesium oxide dispersed therein and has a thickness of 10 μm. The multilayer material was stored in a nitrogen environment so that moisture absorption would not proceed, and the corrosion start time, internal haze, storage elastic modulus, and adhesion of the Ca film were evaluated in accordance with the evaluation method described above.

[Comparative Example 4]

(C4-1. Production of resin film)

A bead mill was used to mix and mix hydrotalcite particles (the number of primary particles in a dispersed state, an average particle diameter of 600 nm, a refractive index (n2) of 1.51), 10 g, a dispersant having an acidic adsorption group, and 180 g of cyclohexane to make 5% water. Talc dispersion liquid C4. Next, 40 g of the particles (vi) obtained in (1-2) of Example 1 and 160 g of cyclohexane were mixed, and the particles were dissolved to prepare a 20% polymer solution.

The hydrotalcite dispersion liquid C4 and the polymer solution were weighed at a ratio of 1: 2 and mixed to prepare a polymer solution containing hydrotalcite. This polymer solution containing hydrotalcite was applied to a release-treated PET film using a device, and dried on a hot plate at 110 ° C. for 3 minutes to evaporate the solvent. By this operation, a multilayered article including a release-treated PET film and a resin film formed thereon was obtained. The resin film in the multilayer contains 10% of hydrotalcite dispersed therein and has a thickness of 10 μm. The multilayer material was stored in a nitrogen environment so that moisture absorption would not proceed, and the corrosion start time, internal haze, storage elastic modulus, and adhesion of the Ca film were evaluated in accordance with the evaluation method described above.

The evaluation results are shown in Tables 1 and 2 (hereinafter sometimes collectively referred to as "tables").

The "corrosion time (hour)" in the table means the corrosion start time of the Ca film, and the "adhesion" in the table means the adhesion test. In the table, the column of the result of closeness reveals the ratio of the number of checkerboards remaining without being stripped to the number of checkerboards (the number of checkerboards remaining without being peeled off / the number of full checkers) relative to the total number of checkerboards. The column for the evaluation of adhesion shows the results evaluated by the above evaluation criteria.

In Tables 1 and 2, the evaluation results are disclosed, and the type of the silane-modified polymer in the resin used in each example, the refractive index of the resin (n1), the type of hygroscopic particles, and the resin film are also disclosed. Concentration, the refractive index (n2) and the primary particle diameter of the hygroscopic particles, the absolute value of the difference between the refractive index of the resin and the refractive index of the hygroscopic particles (| n1−n2 |), and 100 parts by weight relative to the hygroscopic particles The amount (parts by weight) of the dispersant and the thickness of the resin film.

The "silane-modified SIS" in the table means "a silane-modified product of a hydrogenated styrene-isoprene-styrene block copolymer".

『表 1』 Table 1

『Table 2』 Table 2

The resin films obtained in Examples 1 to 3 have characteristics of so-called high transparency and excellent adhesion while preventing moisture intrusion, thereby obtaining a sealing film for use as an electronic device.

no.

Claims (15)

A resin film for an electronic device, comprising: a polymer-containing resin; hygroscopic particles and a dispersant dispersed in the resin and having a primary particle diameter of 200 nm or less; wherein the refractive index of the resin is different from the particles The absolute value is 0.05 or less. The resin film for an electronic device according to claim 1, wherein the resin is a thermoplastic resin. The resin film for an electronic device according to claim 2, wherein the thermoplastic resin is a thermoplastic elastomer. The resin film for an electronic device according to claim 1, wherein the polymer is one or more selected from the group consisting of an aromatic vinyl compound-conjugated diene copolymer and a hydrogenated aromatic vinyl compound-conjugated diene copolymer. The resin film for an electronic device according to claim 4, wherein the aromatic vinyl compound-conjugated diene copolymer is an aromatic vinyl compound-conjugated diene block copolymer. The resin film for electronic devices according to claim 5, wherein the aromatic vinyl compound-conjugated diene block copolymer is selected from the group consisting of styrene-butadiene block copolymer, styrene-butadiene-benzene One or more of an ethylene block copolymer, a styrene-isoprene block copolymer, and a styrene-isoprene-styrene block copolymer. The resin film for electronic devices according to claim 4, wherein the hydrogenated aromatic vinyl compound-conjugated diene copolymer is a hydrogenated aromatic vinyl compound-conjugated diene block copolymer. The resin film for electronic devices according to claim 7, wherein the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is selected from hydrogenated styrene-butadiene block copolymer, hydrogenated styrene- One or more of a butadiene-styrene block copolymer, a hydrogenated styrene-isoprene block copolymer, and a hydrogenated styrene-isoprene-styrene block copolymer. The resin film for an electronic device according to claim 7, wherein the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is a hydrogenated hydrogenation of both an unsaturated bond of a conjugated diene and an aromatic ring. Aromatic ethylene compound-conjugated diene block copolymer. The resin film for an electronic device according to claim 1, wherein the resin contains a polymer having a polar group as the polymer. The resin film for an electronic device according to claim 10, wherein the polymer having a polar group is a graft polymer containing a polar group-containing unit. The resin film for an electronic device according to claim 1, which has a storage elastic modulus at 25 ° C of 10 ⁷ Pa or more and 10 ⁹ Pa or less. The resin film for an electronic device according to claim 1, which has a thickness of 0.1 μm to 1,000 μm. The resin film for an electronic device according to any one of claims 1 to 13, which has an internal haze of 6.0% or less. An electronic device comprising the resin film for an electronic device according to any one of claims 1 to 14.